U.S. patent number 9,708,682 [Application Number 14/650,387] was granted by the patent office on 2017-07-18 for production method for grain-oriented electrical steel sheet.
This patent grant is currently assigned to JFE STEEL CORPORATION. The grantee listed for this patent is JFE STEEL CORPORATION. Invention is credited to Yasuyuki Hayakawa, Hiroshi Matsuda, Yukihiro Shingaki, Yuiko Wakisaka, Hiroi Yamaguchi.
United States Patent |
9,708,682 |
Hayakawa , et al. |
July 18, 2017 |
Production method for grain-oriented electrical steel sheet
Abstract
Grain-oriented electrical steel sheets with good magnetic
properties are industrially stably produced, by using as the
material, a steel slab having a predetermined composition, wherein
after cold rolling and before the start of secondary
recrystallization annealing, the cold rolled sheet is subjected to
nitriding treatment with nitrogen content of 50 mass ppm or more
and 1000 mass ppm or less, and a total content of 0.2 mass % to 15
mass % of a sulfide and/or sulfate is contained in an annealing
separator, and a staying time in the temperature range of
300.degree. C. to 800.degree. C. in the heating stage of secondary
recrystallization annealing of 5 hours or more is secured to
precipitate silicon nitride (Si.sub.3N.sub.4) and MnS, and using
the silicon nitride in combination with MnS as inhibiting force for
normal grain growth to significantly reduce variation of magnetic
properties.
Inventors: |
Hayakawa; Yasuyuki (Asakuchi,
JP), Shingaki; Yukihiro (Kurashiki, JP),
Yamaguchi; Hiroi (Kurashiki, JP), Matsuda;
Hiroshi (Chiba, JP), Wakisaka; Yuiko (Kurashiki,
JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
JFE STEEL CORPORATION |
Tokyo |
N/A |
JP |
|
|
Assignee: |
JFE STEEL CORPORATION (Tokyo,
JP)
|
Family
ID: |
51021448 |
Appl.
No.: |
14/650,387 |
Filed: |
December 25, 2013 |
PCT
Filed: |
December 25, 2013 |
PCT No.: |
PCT/JP2013/085321 |
371(c)(1),(2),(4) Date: |
June 08, 2015 |
PCT
Pub. No.: |
WO2014/104393 |
PCT
Pub. Date: |
July 03, 2014 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20150299819 A1 |
Oct 22, 2015 |
|
Foreign Application Priority Data
|
|
|
|
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Dec 28, 2012 [JP] |
|
|
2012-288612 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C22C
38/008 (20130101); C21D 6/002 (20130101); C21D
6/004 (20130101); C22C 38/16 (20130101); H01F
41/02 (20130101); C21D 8/1222 (20130101); C21D
8/1272 (20130101); C21D 8/1283 (20130101); C23C
8/50 (20130101); H01F 1/14783 (20130101); C22C
38/12 (20130101); C22C 38/34 (20130101); C21D
6/005 (20130101); C21D 8/1255 (20130101); C22C
38/48 (20130101); C22C 38/02 (20130101); C23C
8/04 (20130101); C23C 8/26 (20130101); C22C
38/42 (20130101); C22C 38/60 (20130101); C22C
38/001 (20130101); C21D 1/26 (20130101); C21D
8/1261 (20130101); C23C 8/02 (20130101); C22C
38/002 (20130101); C22C 38/06 (20130101); C23C
8/80 (20130101); H01F 1/16 (20130101); C21D
6/008 (20130101); C22C 38/44 (20130101); C22C
38/26 (20130101); C21D 8/1233 (20130101); C22C
38/20 (20130101); C22C 38/22 (20130101); C21D
6/001 (20130101); C21D 9/46 (20130101); C22C
38/04 (20130101); C22C 38/08 (20130101) |
Current International
Class: |
C21D
8/12 (20060101); C22C 38/44 (20060101); C22C
38/48 (20060101); C23C 8/04 (20060101); H01F
1/147 (20060101); H01F 41/02 (20060101); C22C
38/16 (20060101); C22C 38/22 (20060101); C23C
8/02 (20060101); C23C 8/80 (20060101); C21D
1/26 (20060101); C21D 6/00 (20060101); C21D
9/46 (20060101); C22C 38/06 (20060101); C22C
38/20 (20060101); C22C 38/26 (20060101); C22C
38/34 (20060101); C22C 38/42 (20060101); C23C
8/26 (20060101); C23C 8/50 (20060101); C22C
38/60 (20060101); H01F 1/16 (20060101); C22C
38/00 (20060101); C22C 38/02 (20060101); C22C
38/04 (20060101); C22C 38/08 (20060101); C22C
38/12 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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|
|
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|
1242057 |
|
Jan 2000 |
|
CN |
|
1400319 |
|
Mar 2003 |
|
CN |
|
S40-015644 |
|
Jul 1965 |
|
JP |
|
S51-013469 |
|
Apr 1976 |
|
JP |
|
H06-158167 |
|
Jun 1994 |
|
JP |
|
2782086 |
|
Jul 1998 |
|
JP |
|
2000-129356 |
|
May 2000 |
|
JP |
|
2001-107147 |
|
Apr 2001 |
|
JP |
|
2006-152364 |
|
Jun 2006 |
|
JP |
|
2007-314823 |
|
Dec 2007 |
|
JP |
|
Other References
Jan. 15, 2016 Office Action issued in Korean Patent Application No.
2015-7019245 (with concise statement of relevance). cited by
applicant .
Apr. 8, 2014 International Search Report issued in International
Application No. PCT/JP2013/085321. cited by applicant .
Sep. 23, 2016 Office Action issued in Chinese Patent Application
No. 201380068330.8. cited by applicant .
Sep. 23, 2016 Search Report issued in Chinese Patent Application
No. 201380068330.8. cited by applicant .
Jun. 1, 2016 Office Action issued in Chinese Patent Application No.
201380068330.8. cited by applicant.
|
Primary Examiner: Roe; Jessee
Attorney, Agent or Firm: Oliff PLC
Claims
The invention claimed is:
1. A production method for a grain-oriented electrical steel sheet,
the method comprising: subjecting a steel slab to hot rolling,
without re-heating or after re-heating, to obtain a hot rolled
sheet, the steel slab having a composition containing, by mass % or
mass ppm, C: 0.08% or less, Si: 2.0% to 4.5% and Mn: 0.5% or less,
S: less than 50 ppm, Se: less than 50 ppm, O: less than 50 ppm,
sol.Al: 80 ppm or less, N in a range satisfying
[sol.Al].times.(14/27) ppm.ltoreq.N.ltoreq.80 ppm, and the balance
being Fe and incidental impurities; then subjecting the hot rolled
sheet to annealing and cold rolling to obtain a cold rolled sheet
of final sheet thickness; then subjecting the cold rolled sheet to
primary recrystallization annealing; then applying an annealing
separator thereon; and then subjecting the cold rolled sheet to
secondary recrystallization annealing, wherein after cold rolling
and before the start of secondary recrystallization annealing, the
cold rolled sheet is subjected to nitriding treatment to obtain a
nitrogen content of 50 mass ppm or more and 1000 mass ppm or less,
the annealing separator contains 50 mass % or more of MgO and a
total content of 0.2 mass % to 15 mass % of a sulfide and/or
sulfate, and a staying time in the temperature range of 300.degree.
C. to 800.degree. C. in the heating stage of the secondary
recrystallization annealing of 5 hours or more is secured.
2. The production method for a grain-oriented electrical steel
sheet according to claim 1, wherein the sulfide and/or sulfate is a
sulfide and/or sulfate of one or more of Ag, Al, La, Ca, Co, Cr,
Cu, Fe, In, K, Li, Mg, Mn, Na, Ni, Sn, Sb, Sr, Zn and Zr.
3. The production method for a grain-oriented electrical steel
sheet according to claim 1, wherein the composition of the steel
slab further contains, by mass %, one or more of Ni: 0.005% to
1.50%, Sn: 0.01% to 0.50%, Sb: 0.005% to 0.50%, Cu: 0.01% to 0.50%,
Cr: 0.01% to 1.50%, P: 0.0050% to 0.50%, Mo: 0.01% to 0.50% and Nb:
0.0005% to 0.0100%.
4. The production method for a grain-oriented electrical steel
sheet according to claim 2, wherein the composition of the steel
slab further contains, by mass %, one or more of Ni: 0.005% to
1.50%, Sn: 0.01% to 0.50%, Sb: 0.005% to 0.50%, Cu: 0.01% to 0.50%,
Cr: 0.01% to 1.50%, P: 0.0050% to 0.50%, Mo: 0.01% to 0.50% and Nb:
0.0005% to 0.0100%.
5. The production method for a grain-oriented electrical steel
sheet according to claim 1, wherein the total content of the
sulfide and/or sulfate contained in the annealing separator is 2
mass % to 15 mass %.
Description
TECHNICAL FIELD
The present invention relates to a production method for a
grain-oriented electrical steel sheet with excellent magnetic
properties which enables obtaining a grain-oriented electrical
steel sheet with excellent magnetic properties at low cost.
BACKGROUND
A grain oriented electrical steel sheet is a soft magnetic material
used as an iron core material of transformers, generators, and the
like, and has a crystal orientation in which the <001>
direction, which is an easy magnetization axis of iron, is highly
accorded with the rolling direction of the steel sheet. Such
microstructure is formed through secondary recrystallization where
coarse crystal grains with (110)[001] orientation or the so-called
Goss orientation grows preferentially, during secondary
recrystallization annealing in the production process of the
grain-oriented electrical steel sheet.
Conventionally, such grain-oriented electrical steel sheets have
been manufactured by heating a slab containing around 4.5 mass % or
less of Si and inhibitor components such as MnS, MnSe and AlN to
1300.degree. C. or higher, and then dissolving the inhibitor
components once, and then subjecting the slab to hot rolling to
obtain a hot rolled steel sheet, and then subjecting the steel
sheet to hot band annealing as necessary, and subsequent cold
rolling once, or twice or more with intermediate annealing
performed therebetween until reaching final sheet thickness, and
then subjecting the steel sheet to primary recrystallization
annealing in wet hydrogen atmosphere, and subsequent primary
recrystallization and decarburization, and then applying an
annealing separator mainly composed of magnesia (MgO) thereon and
performing final annealing at 1200.degree. C. for around 5 hours
for secondary recrystallization and purification of inhibitor
components (e.g. see U.S. Pat. No. 1,965,559A (PTL 1), JPS4015644B
(PTL 2) and JPS5113469B (PTL 3))
As mentioned above, in the conventional production processes of
grain-oriented electrical steel sheets, precipitates such as MnS,
MnSe and AlN precipitates (inhibitor components) are contained in a
slab, which is then heated at a high temperature exceeding
1300.degree. C. to dissolve these inhibitor components once, and in
the following process, the inhibitor components are finely
precipitated to cause secondary recrystallization. As described
above, in the conventional production processes of grain-oriented
electrical steel sheets, since slab heating at a high temperature
exceeding 1300.degree. C. was required, significantly high
manufacturing costs were inevitable and therefore recent demands of
reduction in manufacturing costs could not be met.
In order to solve the above problem, for example, JP2782086B (PTL
4) proposes a method including preparing a slab containing 0.010%
to 0.060% of acid-soluble Al (sol.Al), heating the slab at a low
temperature, and performing nitridation in a proper nitriding
atmosphere during the decarburization annealing process to form a
precipitate of (Al,Si)N during secondary recrystallization to be
used as an inhibitor. (Al,Si)N finely disperses in steel and serves
as an effective inhibitor. However, since inhibitor strength is
determined by the content of Al, there were cases where a
sufficient grain growth suppressing effect could not be obtained
when the hitting accuracy of Al amount during steelmaking was
insufficient. Many methods similar to the above where nitriding
treatment is performed during intermediate process steps and
(Al,Si)N or AlN is used as an inhibitor have been proposed and,
recently, production methods where the slab heating temperature
exceeds 1300.degree. C. have also been disclosed.
On the other hand, investigation has also been made on techniques
for causing secondary recrystallization without containing
inhibitor components in the slab from the start. For example, as
disclosed in JP2000129356A (PTL 5), a technique enabling secondary
recrystallization without containing inhibitor components, a
so-called inhibitor-less method was developed. This inhibitor-less
method is a technique to use a highly purified steel and to cause
secondary recrystallization by means of texture control.
In this inhibitor-less method, high-temperature slab heating is
unnecessary, and it is possible to produce grain-oriented
electrical steel sheets at low cost. However, this method is
characterized in that, due to the absence of an inhibitor, magnetic
properties of the products were likely to vary with temperature
variation in intermediate process steps during manufacture. Texture
control is an important factor in this technique and, accordingly,
many techniques for texture control, such as warm rolling, have
been proposed. However, when textures are not sufficiently
controlled, the degree to which grains are accorded with the Goss
orientation ((110)[001] orientation) after secondary
recrystallization tend to be lower compared to when utilizing
techniques using inhibitors, resulting in the lower magnetic flux
density.
CITATION LIST
Patent Literature
PTL 1: U.S. Pat. No. 1,965,559A
PTL 2: JPS4015644B
PTL 3: JPS5113469B
PTL 4: JP2782086B
PTL 5: JP2000129356A
As mentioned above, with production methods for grain-oriented
electrical steel sheets using an inhibitor-less method so far
proposed, it was not always easy to stably obtain good magnetic
properties.
By using components with Al content reduced to less than 100 ppm,
equivalent to inhibitor-less components, avoiding high-temperature
slab heating, and performing nitridation to precipitate silicon
nitride (Si.sub.3N.sub.4) rather than AlN, and further containing a
sulfide and/or sulfate in an annealing separator to precipitate
MnS, and by inhibiting normal grain growth using the silicon
nitride and the MnS, the present invention enables significantly
reducing variation of magnetic properties to industrially stably
produce grain-oriented electrical steel sheets with good magnetic
properties.
SUMMARY
In order to obtain a grain-oriented electrical steel sheet with
reduced variation in magnetic properties while suppressing the slab
heating temperature, the inventors of the present invention used an
inhibitor-less method to prepare a primary recrystallized texture,
precipitated silicon nitride thereon by performing nitridation
during an intermediate process step, and carried out investigation
on using the silicon nitride as an inhibitor.
The inventors inferred that, if it is possible to precipitate
silicon, which is normally contained in an amount of several % in a
grain-oriented electrical steel sheet, as silicon nitride so as to
be used as an inhibitor, a grain growth inhibiting effect would
work equally well regardless of the amount of other nitride-forming
elements (Al, Ti, Cr, V, etc.) by controlling the degree of
nitridation at the time of nitriding treatment.
On the other hand, unlike (Al,Si)N in which Si is dissolved in AlN,
pure silicon nitride has poor matching with the crystal lattice of
steel and has a complicated crystal structure with covalent bonds.
Accordingly, it is known that to finely precipitate pure silicon
nitride in grains is extremely difficult. For this reason, it
follows that it would be difficult to finely precipitate pure
silicon nitride in grains after performing nitridation as in
conventional methods.
However, the inventors inferred that, by taking advantage of this
characteristic, it would be possible to suppress precipitation of
silicon nitride in grains and selectively precipitate silicon
nitride at grain boundaries. Further, the inventors believed that,
if it is possible to selectively precipitate silicon nitride at
grain boundaries, a sufficient grain growth inhibiting effect would
be obtained even in the presence of coarse precipitates.
Further, the inventors inferred that, by containing a sulfide
and/or sulfate in an annealing separator to form MnS and by using
them in combination with silicon nitride, the grain growth
inhibiting effect can be further improved.
Based on the above ideas, the inventors conducted intense
investigations starting from chemical compositions of the material,
and extending to the nitrogen content after nitriding treatment,
heat treatment conditions, components of the annealing separator
for forming silicon nitride by diffusing nitrogen along grain
boundaries, and the like.
As a result, the inventors discovered a new usage of silicon
nitride in combination with MnS, and completed the present
invention.
Specifically, the primary features of the present invention are as
follows.
1. A production method for a grain-oriented electrical steel sheet,
the method comprising: subjecting a steel slab to hot rolling,
without re-heating or after re-heating, to obtain a hot rolled
sheet, the steel slab having a composition consisting of, by mass %
or mass ppm, C: 0.08% or less, Si: 2.0% to 4.5% and Mn: 0.5% or
less, S: less than 50 ppm, Se: less than 50 ppm, O: less than 50
ppm, sol.Al: less than 100 ppm, N in a range satisfying
[sol.Al].times.(14/27) ppm.ltoreq.N.ltoreq.80 ppm, and the balance
being Fe and incidental impurities; then subjecting the hot rolled
sheet to annealing and cold rolling to obtain a cold rolled sheet
of final sheet thickness; then subjecting the cold rolled sheet to
primary recrystallization annealing; then applying an annealing
separator thereon; and then subjecting the cold rolled sheet to
secondary recrystallization annealing,
wherein after cold rolling and before the start of secondary
recrystallization annealing, the cold rolled sheet is subjected to
nitriding treatment to obtain a nitrogen content of 50 mass ppm or
more and 1000 mass ppm or less,
a total content of 0.2 mass % to 15 mass % of a sulfide and/or
sulfate is contained in an annealing separator, and
a staying time in the temperature range of 300.degree. C. to
800.degree. C. in the heating stage of the secondary
recrystallization annealing of 5 hours or more is secured,
2. The production method for a grain-oriented electrical steel
sheet according to aspect 1, wherein the sulfide and/or sulfate is
a sulfide and/or sulfate of one or more of Ag, Al, La, Ca, Co, Cr,
Cu, Fe, In, K, Li, Mg, Mn, Na, Ni, Sn, Sb, Sr, Zn and Zr.
3. The production method for a grain-oriented electrical steel
sheet according to aspect 1 or 2, wherein the composition of the
steel slab further contains, by mass %, one or more of Ni: 0.005%
to 1.50%, Sn: 0.01% to 0.50%, Sb: 0.005% to 0.50%, Cu: 0.01% to
0.50%, Cr: 0.01% to 1.50%, P: 0.0050% to 0.50%, Mo: 0.01% to 0.50%
and Nb: 0.0005% to 0.0100%.
According to the present invention, it is possible to industrially
stably produce grain-oriented electrical steel sheets having good
magnetic properties with significantly reduced variation, without
the need of high-temperature slab heating.
Further, in the present invention, pure silicon nitride which is
not precipitated compositely with Al is used compositely with MnS,
and therefore when performing purification, it is possible to
achieve purification of steel simply by purifying only nitrogen and
sulfur, which diffuse relatively quickly.
Further, when using Al or Ti as precipitates as in conventional
methods, control in ppm order was necessary from the perspective of
achieving desired purification and guaranteeing an inhibitor
effect. However, when using Si and S as precipitates during
intermediate process steps as in the present invention, such
control is completely unnecessary during steelmaking.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be further described below with
reference to the accompanying drawings, wherein:
FIG. 1 shows electron microscope photographs of a microstructure
subjected to decarburization annealing, followed by nitriding
treatment such that the nitrogen content is 100 mass ppm (FIG. 1A)
or 500 mass ppm (FIG. 1B), subsequently heated to 800.degree. C. at
a predetermined heating rate, and then immediately subjected to
water-cooling, as well as a graph (FIG. 1C) showing the
identification results of precipitates in the above microstructure
obtained by EDX (energy-dispersive X-ray spectrometry).
DETAILED DESCRIPTION
Details of the present invention are described below.
First, reasons for limiting the chemical compositions of the steel
slab to the aforementioned range in the present invention will be
explained. Here, unless otherwise specified, indications of "%" and
"ppm" regarding components shall each stand for mass % and mass
ppm.
C: 0.08% or less
C is a useful element in terms of improving primary recrystallized
textures. However, if the content thereof exceeds 0.08%, primary
recrystallized textures deteriorate. Therefore, C content is
limited to 0.08% or less. From the viewpoint of magnetic
properties, the preferable C content is in the range of 0.01% to
0.06%. If the required level of magnetic properties is not very
high, C content may be set to 0.01% or less for the purpose of
omitting or simplifying decarburization during primary
recrystallization annealing.
Si; 2.0% to 4.5%
Si is a useful element which improves iron loss properties by
increasing electrical resistance. However, if the content thereof
exceeds 4.5%, it causes significant deterioration of cold rolling
manufacturability, and therefore Si content is limited to 4.5% or
less. On the other hand, for enabling Si to function as a
nitride-forming element, Si content needs to be 2.0% or more.
Further, from the viewpoint of iron loss properties, the preferable
Si content is in the range of 2.0% to 4.5%,
Mn: 0.5% or less
Since Mn provides an effect of improving hot workability during
manufacture, it is preferably contained in the amount of 0.03% or
more. However, if the content thereof exceeds 0.5%, primary
recrystallized textures worsen and magnetic properties deteriorate.
Therefore, Mn content is limited to 0.5% or less.
S, Se and O: less than 50 ppm (individually)
If the content of each of S, Se and O is 50 ppm or more, it becomes
difficult to develop secondary recrystallization. This is because
primary recrystallized textures are made non-uniform by coarse
oxides or MnS and MnSe coarsened by slab heating. Therefore, S, Se
and O are all suppressed to less than 50 ppm. The contents of these
elements may also be 0 ppm.
sol,Al: less than 100 ppm
Al forms a dense oxide film on a surface of the steel sheet, and
could make it difficult to control the degree of nitridation at the
time of nitriding treatment or obstruct deearburization. Therefore,
Al content is suppressed to less than 100 ppm in terms of sol.Al.
However, Al, which has high affinity with oxygen, is expected to
bring about such effects as to reduce the amount of dissolved
oxygen in steel and to reduce oxide inclusions which would lead to
deterioration of magnetic properties, when added in minute
quantities during steelmaking. Therefore, in order to curb
deterioration of magnetic properties, it is advantageous to add Al
in an amount of 20 ppm or more. The content thereof may also be 0
ppm. [sol.Al].times.(14/27)ppm.ltoreq.N.ltoreq.80 ppm
The present invention has a feature that silicon nitride is
precipitated after performing nitridation. Therefore, it is
important that N is contained beforehand in steel in an amount
equal to or more than the N content required to precipitate as AlN
with respect to the amount of Al contained in steel. In particular,
since Al and N are bonded at a ratio of 1:1, by containing N in an
amount satisfying (sol.Al (mass ppm)).times.[atomic weight of N
(14)/atomic weight of Al (27)] or more, it is possible to
completely precipitate a minute amount of Al contained in steel
before nitriding treatment. On the other hand, since N could become
the cause of defects such as blisters at the time of slab heating,
N content needs to be suppressed to 80 ppm or less. The content
thereof is preferably 60 ppm or less.
The basic components are as described above. In the present
invention, the following elements may be contained according to
necessity as components for improving magnetic properties in an
even more industrially reliable manner.
Ni: 0.005% to 1.50%
Ni provides an effect of improving magnetic properties by enhancing
the uniformity of texture of the hot rolled sheet, and, to obtain
this effect, it is preferably contained in an amount of 0.005% or
more. On the other hand, if Ni content exceeds 1.50%, it becomes
difficult to develop secondary recrystallization, and magnetic
properties deteriorate. Therefore, Ni is preferably contained in a
range of 0.005% to 1.50%,
Sn: 0.01% to 0.50%
Sn is a useful element which improves magnetic properties by
suppressing nitridation and oxidization of the steel sheet during
secondary recrystallization annealing and facilitating secondary
recrystallization of crystal grains having good crystal
orientation, and to obtain this effect, it is preferably contained
in an amount of 0.01% or more. On the other hand, if Sn is
contained in an amount exceeding 0.50%, cold rolling
manufacturability deteriorates. Therefore, Sn is preferably
contained in the range of 0.01% to 0.50%.
Sb: 0.005% to 0.50%
Sb is a useful element which effectively improves magnetic
properties by suppressing nitridation and oxidization of the steel
sheet during secondary recrystallization annealing and facilitating
secondary recrystallization of crystal grains having good crystal
orientation, and to obtain this effect, it is preferably contained
in an amount of 0.005% or more. On the other hand, if Sb is
contained in an amount exceeding 0.50%, cold rolling
manufacturability deteriorates. Therefore, Sb is preferably
contained in the range of 0.005% to 0.50%.
Cu: 0.01% to 0.50%
Cu provides an effect of effectively improving magnetic properties
by suppressing oxidization of the steel sheet during secondary
recrystallization annealing and facilitating secondary
recrystallization of crystal grains having good crystal
orientation, and to obtain this effect, it is preferably contained
in an amount of 0.01% or more. On the other hand, if Cu is
contained in an amount exceeding 0.50%, hot rolling
manufacturability deteriorates. Therefore, Cu is preferably
contained in the range of 0.01% to 0.50%,
Cr: 0.01% to 1.50%
Cr provides an effect of stabilizing formation of forsterite films,
and, to obtain this effect, it is preferably contained in an amount
of 0.01% or more. On the other hand, if Cr content exceeds 1.50%,
it becomes difficult to develop secondary recrystallization, and
magnetic properties deteriorate. Therefore, Cr is preferably
contained in the range of 0.01% to 1.50%.
P: 0.0050% to 0.50%
P provides an effect of stabilizing formation of forsterite films,
and, to obtain this effect, it is preferably contained in an amount
of 0.0050% or more. On the other hand, if P content exceeds 0.50%,
cold rolling manufacturability deteriorates. Therefore, P is
preferably contained in a range of 0.0050% to 0.50%.
Mo: 0.01% to 0.50%, Nb: 0.0005% to 0.0100%
Mo and Nb both have an effect of suppressing generation of scabs
after hot rolling by for example, suppressing cracks caused by
temperature change during slab heating. These elements become less
effective for suppressing scabs, however, unless Mo content is
0.01% or more and Nb content is 0.0005% or more. On the other hand,
if Mo content exceeds 0.50% and Nb content exceeds 0.0100%, they
cause deterioration of iron loss properties if they remain in the
finished product as, for example, carbide or nitride. Therefore, it
is preferable for each of Mo content and Nb content to be within
the above mentioned ranges.
Next, the production method for the present invention will be
explained.
A steel slab adjusted to the above preferable chemical composition
range is subjected to hot rolling without being re-heated or after
being re-heated. When re-heating the slab, the re-heating
temperature is preferably approximately in the range of
1000.degree. C. to 1300.degree. C. This is because slab heating at
a temperature exceeding 1300.degree. C. is not effective in the
present invention where little inhibitor element is contained in
steel in the form of a slab, and only causes an increase in costs,
while slab heating at a temperature of lower than 1000.degree. C.
increases the rolling load, which makes rolling difficult.
Then, the hot rolled sheet is subjected to hot band annealing as
necessary, and subsequent cold rolling once, or twice or more with
intermediate annealing performed therebetween to obtain a final
cold rolled sheet.
The cold rolling may be performed at room temperature.
Alternatively, warm rolling where rolling is performed with the
steel sheet temperature raised to a temperature higher than room
temperature for example, around 250.degree. C. is also
applicable.
Then, the final cold rolled sheet is subjected to primary
recrystallization annealing.
The purpose of primary recrystallization annealing is to anneal the
cold rolled sheet with a rolled microstructure for primary
recrystallization to adjust the grain size of the primary
recrystallized grains so that they are of optimum grain size for
secondary recrystallization. In order to do so, it is preferable to
set the annealing temperature of primary recrystallization
annealing approximately in the range of 800.degree. C. to below
950.degree. C. Further, by setting the annealing atmosphere during
primary recrystallization annealing to an atmosphere of wet
hydrogen-nitrogen or wet hydrogen-argon, primary recrystallization
annealing may be combined with decarburization annealing.
Further, in the present invention, nitriding treatment is performed
after the above cold rolling and before the start of secondary
recrystallization annealing. As long as the degree of nitridation
is controlled, any means of nitridation can be used and there is no
particular limitation. For example, as performed in the past, gas
nitriding may be performed directly in the form of a coil using
NH.sub.3 atmosphere gas, or continuous nitriding may be performed
on a running strip. Here, preferable treatment conditions are a
treatment temperature of 600.degree. C. to 800.degree. C. and a
treatment time of 10 seconds to 300 seconds. Further, it is also
possible to utilize salt bath nitriding treatment with higher
nitriding ability than gas nitriding. Here, a preferred salt bath
is a salt bath of an NaCN--Na.sub.2CO.sub.3--NaCl system. Here, the
preferable treatment conditions are a salt bath temperature of
400.degree. C. to 700.degree. C. and a treatment time of 10 seconds
to 300 seconds.
The important point of the above nitriding treatment is the
formation of a nitride layer on the surface layer. In order to
suppress diffusion into steel, it is preferable to perform
nitriding treatment at a temperature of 800.degree. C. or lower,
yet, by shortening the duration of the treatment (e.g. to around 30
seconds), it is possible to form a nitride layer only on the
surface even if the treatment is performed at a higher
temperature.
Here, it is necessary for the nitrogen content after performing
nitridation to be 50 mass ppm or more and 1000 mass ppm or less. If
the nitrogen content is less than 50 mass ppm, a sufficient effect
cannot be obtained, whereas if it exceeds 1000 mass ppm, an
excessive amount of silicon nitride precipitates and secondary
recrystallization hardly occurs. Preferably, the nitrogen content
is in a range of 200 mass ppm to less than 1000 mass ppm.
After subjecting the steel sheet to the above primary
recrystallization annealing and nitriding treatment, an annealing
separator is applied on a surface of the steel sheet. In order to
form a forsterite film on the surface of the steel sheet after
secondary recrystallization annealing, it is necessary to use an
annealing separator mainly composed of magnesia (MgO). However, if
there is no need to form a forsterite any suitable oxide with a
melting point higher than the secondary recrystallization annealing
temperature, such as alumina (Al.sub.2O.sub.3) or calcia (CaO), can
be used as the main component of the annealing separator.
An annealing separator mainly composed of magnesia (MgO) refers to
an annealing separator containing magnesia (MgO) of 50 mass % or
more, preferably 80 mass % or more.
Here, it is important to contain a sulfide and/or sulfate in an
annealing separator in an amount of 0.2 mass % to 15 mass %, in
order to form MnS during secondary recrystallization annealing to
obtain a grain growth inhibiting effect, thereby increasing the
intensity of the Goss orientation which is an ideal orientation of
secondary recrystallization.
This is because if the content of a sulfide and/or sulfate in an
annealing separator is less than 0.2 mass %, the above effect is
not obtained, whereas if the content thereof exceeds 15 mass %,
base film formation becomes difficult.
Therefore, the content of a sulfide and/or sulfate in an annealing
separator is in the range of 0.2 mass % to 15 mass %. The range is
preferably 2 mass % to 10 mass %.
Further, if Cu is contained as a steel component, CuS precipitates
as a sulfide in addition to MnS and, as is the case with MnS,
contributes to improving the grain growth inhibiting effect.
Further, as a sulfide and/or sulfate to add to an annealing
separator, a sulfide and/or sulfate of one or more of Ag, Al, La,
Ca, Co, Cr, Cu, Fe, in, K, Li, Mg, Mn, Na, Ni, Sn, Sb, Sr, Zn and
Zr is/are preferable.
Subsequently, secondary recrystallization annealing is performed.
During this secondary recrystallization annealing, it is necessary
to secure a staying time in the temperature range of 300.degree. C.
to 800.degree. C. in the heating stage of 5 hours or more. During
the staying time, the nitride layer mainly composed of Fe.sub.2N,
Fe.sub.4N in the surface layer formed by nitriding treatment is
decomposed and N diffuses into the steel. As for the chemical
composition of the present invention, Al which is capable of
forming MN does not remain, and therefore N as a grain boundary
segregation element diffuses into steel using grain boundaries as
diffusion paths.
Silicon nitride has poor compatibility with steel (i.e. the misfit
ratio is high), and therefore the precipitation rate is very low.
Nevertheless, since the purpose of precipitation of silicon nitride
is to inhibit normal grain growth, it is necessary to have a
sufficient amount of silicon nitride selectively precipitated at
grain boundaries at the stage of 800.degree. C. at which normal
grain growth proceeds. Regarding this point, silicon nitride cannot
precipitate in grains, yet by setting the staying time in the
temperature range of 300.degree. C. to 800.degree. C. to 5 hours or
more, it is possible to selectively precipitate silicon nitride at
grain boundaries by allowing silicon to be bound to N and Si
diffusing along the grain boundaries. Although an upper limit of
the staying time is not necessarily required, performing annealing
for more than 150 hours is unlikely to increase the effect.
Therefore, the upper limit is preferably set to 150 hours. A more
preferable staying time is in a range of 10 hours to 100 hours.
Further, as the annealing atmosphere, either of N.sub.2, Ar,
H.sub.2 or a mixed gas thereof is applicable.
After the start of decomposition of a sulfide and/or sulfate during
secondary recrystallization annealing, since the diffusion rate of
S is lower than N, diffusion proceeds while forming MnS (and
further CuS) from the surface layer, and the concentration of S in
the surface layer becomes significantly higher than that of
nitride. As a result, grain growth in the surface layer is strongly
inhibited, and secondary recrystallization starts from the inner
parts in the sheet thickness direction. In the surface layer of the
steel sheet, a large texture variation is caused due to the
frictional force between the surface layer and rolls during hot
rolling or cold rolling, and as a result, there is a higher
probability of secondary recrystallized grains with displaced
orientations being generated. Therefore, by enhancing the grain
growth inhibiting effect in the surface layer part, the intensity
of the Goss orientation which is an ideal orientation of secondary
recrystallization grains is significantly increased compared to
nitriding treatment alone,
As described above, with a grain-oriented electrical steel sheet
obtained by applying the above process to a slab that contains a
limited amount of Al in steel, with an excessive amount of N with
respect to AlN precipitation added thereto, and contains little
inhibitor components such as MnS or MnSe, it is possible to
selectively form coarse silicon nitride (with a precipitate size of
100 nm or more), as compared to conventional inhibitors, at grain
boundaries at the stage during the heating stage of secondary
recrystallization annealing before secondary recrystallization
starts, and with the sulfide or sulfate contained in the annealing
separator being decomposed and diffused (luring the secondary
recrystallization annealing, it is possible to allow MnS (and CuS)
to precipitate densely at the surface layer. Although there is no
particular limit on the upper limit of the precipitate size of
silicon nitride, it is preferably 10 .mu.m or less.
FIG. 1 shows electron microscope photographs for observation and
identification of a microstructure subjected to decarburization
annealing, followed by nitriding treatment such that the nitrogen
content is 100 mass ppm ((a) of FIG. 1) or 500 mass ppm ((b) of
FIG. 1), subsequently heated to 800.degree. C. at a heating rate
such that the staying time in the temperature range of 300.degree.
C. to 800.degree. C. is 8 hours, and then immediately subjected to
water-cooling, which were observed and identified using an electron
microscope. Further, graph (c) in FIG. 1 shows the results of
identification of precipitates in the aforementioned microstructure
by EDX (energy-dispersive X-ray spectrometry).
It can be seen from FIG. 1 that unlike fine precipitates
conventionally used (with a precipitate size of smaller than 100
nm), even the smallest one of the coarse silicon nitride
precipitates at the grain boundary has a precipitate size greater
than 100 urn.
The use of pure silicon nitride which is not precipitated
compositely with Al which is a feature of the present invention,
has significantly high stability from the viewpoint of effectively
utilizing Si which exists in steel in order of several % and
provides an effect of improving iron loss properties. That is,
components such as Al or Ti, which have been used in conventional
techniques, have high affinity with nitrogen and provide
precipitates which still remain stable at high temperature.
Therefore, these components tend to remain in steel insistently,
and the remaining components could become the cause of
deteriorating magnetic properties.
However, when using silicon nitride, it is possible to achieve
purification of precipitates which are harmful to magnetic
properties simply by purifying nitrogen and sulfur, which diffuse
relatively quickly. Further, when using Al or Ti, control in ppm
order is necessary from the viewpoint that purification is
eventually required and that an inhibitor effect must surely be
obtained. However, when using Si and S, such control is unnecessary
during steelmaking, and this is also an important feature of the
present invention.
In production, it is clear that utilizing the heating stage of
secondary recrystallization is most effective for precipitation of
silicon nitride in terms of energy efficiency, yet it is also
possible to selectively precipitate silicon nitride at grain
boundaries by utilizing a similar heat cycle. Therefore, in
production, it is also possible to perform silicon nitride
dispersing annealing before time consuming secondary
recrystallization.
After the above secondary recrystallization annealing, it is
possible to further apply and bake an insulating coating on the
surface of the steel sheet. Such an insulating coating is not
limited to a particular type, and any conventionally known
insulating coating is applicable. For example, preferred methods
are described in JPS5079442A and JPS4839338A where a coating liquid
containing phosphate-chromate-colloidal silica is applied on a
steel sheet and then baked at a temperature of around 800.degree.
C.
It is possible to correct the shape of the steel sheet by
flattening annealing, and further to combine the flattening
annealing with baking treatment of the insulating coating.
EXAMPLES
Example 1
A steel slab having a composition containing C: 0.04%, Si: 3.4%,
Mn: 0.08%, S: 0.002%, Se: 0.001%, O: 0.001%, Al: 0.006%, N:
0.0035%, Cu: 0.10%, and Sb: 0.06%, with the balance including Fe
and incidental impurities, was heated at 1200.degree. C. for 30
minutes, and then subjected to hot rolling to obtain a hot rolled
sheet with a thickness of 2.2 mm. Then, the steel sheet was
subjected to annealing at 1065.degree. C. for 1 minute, and
subsequent cold rolling to obtain a final sheet thickness of 0.23
mm. Then, samples of the size of 100 mm.times.400 mm were collected
from the center part of the obtained cold rolled coil, and primary
recrystallization annealing combined with decarburization was
performed in a lab. Then, the samples were subjected to gas
treatment or nitriding treatment by salt bath treatment under the
conditions shown in Table 1 to increase the nitrogen content in
steel.
As the nitriding condition for gas treatment, a mixed atmosphere of
NH.sub.3: 30 vol % and N.sub.2: 70 vol % was used. Further, as the
nitriding condition for salt bath treatment, a ternary system salt
of NaCN--Na.sub.2CO.sub.3--NaCl was used.
The N content of the steel sheet after the above nitriding
treatment was measured.
Then, magnesium sulfate was added under the conditions shown in
Table 1 to an annealing separator mainly composed of MgO and
containing 5% of TiO.sub.2 and made into a water slurry state and
then applied, dried and baked on the samples, and subsequently, the
samples were subjected to final annealing under the conditions
shown in Table 1, and then a phosphate-based insulating tension
coating was applied and baked thereon to obtain products.
For the obtained products, the magnetic flux density B.sub.8 (T) at
a magnetizing force of 800 A/m was evaluated.
TABLE-US-00001 TABLE 1 Annealing Final Annealing Separator
Condition Additive Amount Staying Time in Nitriding Treatment N
Content of Magnesium Temperature Range Magnetic Means of Content of
Temperature Time after Treatment Sulfate of 300.degree. C. to
Properties Treatment Treatment (.degree. C.) (s) (mass ppm) (mass
%) 800.degree. C. (h) B.sub.8 (T) Remarks Condition 1 None -- -- --
35 0 20 1.852 Comparative Example Condition 2 Salt Bath Nitridation
550 120 350 0 20 1.913 Comparative Example Condition 3 Salt Bath
Nitridation 550 120 350 5 20 1.949 Inventive Example Condition 4
Salt Bath Nitridation 550 120 350 5 4 1.906 Comparative Example
Condition 5 Salt Bath Nitridation 550 600 700 10 20 1.940 Inventive
Example Condition 6 Gas Nitridation 750 20 120 0 20 1.909
Comparative Example Condition 7 Gas Nitridation 750 20 120 5 20
1.955 Inventive Example Condition 8 Gas Nitridation 750 80 520 5 20
1.958 Inventive Example Condition 9 Gas Nitridation 750 80 520 10
20 1.963 Inventive Example Condition 10 Gas Nitridation 750 5 40 10
20 1.903 Comparative Example Condition 11 Gas Nitridation 750 3600
2900 10 20 1.777 Comparative Example
As can be seen in Table 1, it is clear that magnetic properties are
improved in the inventive examples compared to those produced in
the conventional inhibitor-less manufacturing process.
Example 2
A steel slab containing components shown in Table 2 (the contents
of S, Se, and O each being less than 50 ppm) was heated at
1200.degree. C. for 20 minutes, subjected to hot rolling to obtain
a hot rolled sheet with a thickness of 2.5 mm, and then the hot
rolled sheet was subjected to annealing at 1050.degree. C. for 1
minute, and then cold rolling to obtain a final sheet thickness of
0.27 mm, and then decarburization annealing where the cold rolled
sheet is retained at an annealing temperature of 840.degree. C. for
2 minutes, in an atmosphere of P(H.sub.2O)/P(H.sub.2)=0.4. Then,
some of the coils were subjected to gas nitriding treatment (in an
atmosphere of NH.sub.3: 30 vol %+N.sub.2: 70 vol %) at 750.degree.
C. for 20 seconds, and the N content of the steel sheets was
measured.
Then, annealing separators, each mainly composed of MgO with 10% of
TiO.sub.2 and 10% of aluminum sulfate added thereto, were mixed
with water, made into slurry state and applied on the steel sheets,
respectively, which in turn were wound into coils and then
subjected to Final annealing at a heating rate where the staying
time in the temperature range of 300.degree. C. to 800.degree. C.
was 30 hours. Then, a phosphate-based insulating tension coating
was applied and baked thereon, and flattening annealing was
performed for the purpose of flattening the resulting steel strips
to obtain products.
Epstein test pieces were collected from the product coils thus
obtained and the magnetic flux density B.sub.8 thereof was
measured. The measurement results are shown in Table 2.
TABLE-US-00002 TABLE 2 Annealing Separator Chemical Composition
Additive Amount Si C Mn sol. Al N Others Gas N Content of Magnesium
Magnetic (mass (mass (mass (mass (mass (mass Nitriding after
Treatment Sulfate Properties No. %) ppm) %) ppm) ppm) %) Treatment
(mass ppm) (mass %) B.sub.8 (T) Remarks 1 3.35 400 0.03 180 70 --
Not 70 0 1.821 Comparative Performed Example 2 3.35 400 0.03 180 70
-- Performed 190 0 1.858 Comparative Example 3 3.35 400 0.03 80 20
-- Not 20 0 1.852 Comparative Performed Example 4 3.35 400 0.03 80
20 -- Performed 140 0 1.895 Comparative Example 5 3.35 400 0.03 80
50 -- Not 50 0 1.885 Comparative Performed Example 6 3.35 400 0.03
80 50 -- Performed 130 8 1.951 Inventive Example 7 1.85 400 0.03 80
50 -- Not 50 0 1.875 Comparative Performed Example 8 1.85 400 0.03
80 50 -- Performed 90 0 1.903 Comparative Example 9 3.35 200 0.1 50
20 -- Not 20 8 1.888 Comparative Performed Example 10 3.35 200 0.1
50 40 -- Performed 150 8 1.945 Inventive Example 11 3.35 600 0.08
60 40 -- Not 40 0 1.878 Comparative Performed Example 12 3.35 600
0.08 60 40 -- Performed 140 8 1.948 Inventive Example 13 3.35 600
0.08 60 40 N: 0.01, Performed 150 8 1.955 Inventive Sb: 0.02
Example 14 3.35 600 0.08 60 40 Sn: 0.03 Performed 150 8 1.954
Inventive Example 15 3.35 600 0.08 60 40 Cr: 0.03, Performed 140 8
1.952 Inventive Mo: 0.05 Example 16 3.35 600 0.08 60 40 Cu: 0.05
Performed 130 8 1.950 Inventive Example 17 3.35 600 0.08 60 40 P:
0.01, Performed 140 8 1.953 Inventive Nb: 0.001 Example
It can be seen from Table 2 that all of the inventive examples
obtained in accordance with the present invention exhibited high
magnetic flux density.
Example 3
A steel slab having a composition containing C: 0.03%, Si: 3.3%,
Mn: 0.09%, S: 0.003%, Se: 0.001%, O: 0.001%, Al: 0.005%, N: 0.003%,
Cu: 0.09% and Sb: 0.05%, with the balance including Fe and
incidental impurities, was heated at 1220.degree. C. for 20
minutes, subjected to hot rolling to obtain a hot rolled sheet with
a thickness of 2.5 mm. Then, the hot rolled sheet was subjected to
annealing at 1050.degree. C. for 1 minute, then cold rolling to
obtain a final sheet thickness of 0.27 mm, and then decarburization
annealing where the cold rolled sheet was retained at an annealing
temperature of 840.degree. C. for 2 minutes, in an atmosphere of
P(H.sub.2O)/P(H.sub.2)=0.4. Then, after performing salt bath
nitriding treatment at 550.degree. C. for 240 seconds (using a
ternary system salt of NaCN--Na.sub.2CO.sub.3--NaCl), the N content
of the steel sheet was measured. The N content was 240 mass
ppm.
Then, annealing separators, each mainly composed of MgO with 10% of
TiO.sub.2 and a sulfide or sulfate added thereto, as shown in Table
3, were mixed with water and made into slurry state and applied on
the steel sheets, respectively, which in turn were wound into coils
and then subjected to final annealing at a heating rate where the
staying time in the temperature range of 300.degree. C. to
800.degree. C. was 30 hours. Then, a phosphate-based insulating
tension coating was applied and baked thereon, and flattening
annealing was performed for the purpose of flattening the steel
strips to obtain products.
Epstein test pieces were collected from the product coils thus
obtained and the magnetic flux density B.sub.8 thereof was
measured. The measurement results are shown in Table 3.
TABLE-US-00003 TABLE 3 Annealing Separator Additive Magnetic Type
of Amount of Properties Sulfide, Sulfide, Sulfate B.sub.8 No.
Sulfate (mass %) (T) Remarks 1 None 0 1.872 Comparative Example 2
Ag.sub.2SO.sub.4 10 1.965 Inventive Example 3
Al.sub.2(SO.sub.4).sub.3 10 1.963 Inventive Example 4 LaSO.sub.4 10
1.955 Inventive Example 5 CaSO.sub.4 10 1.955 Inventive Example 6
CoSO.sub.4 10 1.952 Inventive Example 7 Cr.sub.2(SO.sub.4).sub.2 10
1.954 Inventive Example 8 CuSO.sub.4 10 1.956 Inventive Example 9
FeSO.sub.4 10 1.953 Inventive Example 10 In.sub.2(SO.sub.4).sub.3
10 1.965 Inventive Example 11 K.sub.2SO.sub.4 10 1.952 Inventive
Example 12 Li.sub.2SO.sub.4 10 1.955 Inventive Example 13
MgSO.sub.4 10 1.962 Inventive Example 14 MnSO.sub.4 10 1.961
Inventive Example 15 Na.sub.2SO.sub.4 10 1.957 Inventive Example 16
NiSO.sub.4 10 1.965 Inventive Example 17 SnSO.sub.4 10 1.957
Inventive Example 18 Sb.sub.2(SO.sub.4).sub.3 10 1.958 Inventive
Example 19 SrSO.sub.4 10 1.955 Inventive Example 20 ZnSO.sub.4 10
1.952 Inventive Example 21 Zr(SO.sub.4).sub.2 10 1.950 Inventive
Example 22 MgS 10 1.963 Inventive Example 23 MnS 10 1.955 Inventive
Example 24 Na.sub.2S.sub.2O.sub.3 10 1.956 Inventive Example
It can be seen from Table 3 that all of the inventive examples
obtained in accordance with the present invention exhibited high
magnetic flux density.
* * * * *